EP2820188A1 - Novel method for producing paper implementing a base copolymer having reacted with an aldehyde as a dry strength, retention, drainage and machinability agent - Google Patents
Novel method for producing paper implementing a base copolymer having reacted with an aldehyde as a dry strength, retention, drainage and machinability agentInfo
- Publication number
- EP2820188A1 EP2820188A1 EP13712850.0A EP13712850A EP2820188A1 EP 2820188 A1 EP2820188 A1 EP 2820188A1 EP 13712850 A EP13712850 A EP 13712850A EP 2820188 A1 EP2820188 A1 EP 2820188A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- polymer
- group
- acid
- aldehyde
- base
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 229920001577 copolymer Polymers 0.000 title claims abstract description 67
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 5
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 title abstract 2
- 230000014759 maintenance of location Effects 0.000 title description 6
- 150000001875 compounds Chemical class 0.000 claims abstract description 32
- 239000000178 monomer Substances 0.000 claims abstract description 26
- 238000006243 chemical reaction Methods 0.000 claims abstract description 19
- 125000002091 cationic group Chemical group 0.000 claims abstract description 16
- 125000005842 heteroatom Chemical group 0.000 claims abstract description 8
- 239000000463 material Substances 0.000 claims abstract description 5
- 239000011087 paperboard Substances 0.000 claims abstract description 5
- 239000011111 cardboard Substances 0.000 claims abstract description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 3
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 3
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 3
- 229920002873 Polyethylenimine Polymers 0.000 claims description 35
- 238000000034 method Methods 0.000 claims description 32
- LEQAOMBKQFMDFZ-UHFFFAOYSA-N glyoxal Chemical compound O=CC=O LEQAOMBKQFMDFZ-UHFFFAOYSA-N 0.000 claims description 30
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 18
- 238000006116 polymerization reaction Methods 0.000 claims description 18
- 229940015043 glyoxal Drugs 0.000 claims description 15
- 239000006085 branching agent Substances 0.000 claims description 13
- 229920000768 polyamine Polymers 0.000 claims description 12
- 150000001299 aldehydes Chemical class 0.000 claims description 11
- GQOKIYDTHHZSCJ-UHFFFAOYSA-M dimethyl-bis(prop-2-enyl)azanium;chloride Chemical compound [Cl-].C=CC[N+](C)(C)CC=C GQOKIYDTHHZSCJ-UHFFFAOYSA-M 0.000 claims description 10
- ZIUHHBKFKCYYJD-UHFFFAOYSA-N n,n'-methylenebisacrylamide Chemical compound C=CC(=O)NCNC(=O)C=C ZIUHHBKFKCYYJD-UHFFFAOYSA-N 0.000 claims description 9
- 239000002253 acid Chemical class 0.000 claims description 8
- -1 acrylamidomethylpropyl Chemical group 0.000 claims description 8
- 150000001408 amides Chemical class 0.000 claims description 8
- 239000000654 additive Substances 0.000 claims description 7
- 230000000996 additive effect Effects 0.000 claims description 7
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 6
- 230000015572 biosynthetic process Effects 0.000 claims description 6
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 claims description 6
- 229940088644 n,n-dimethylacrylamide Drugs 0.000 claims description 6
- YLGYACDQVQQZSW-UHFFFAOYSA-N n,n-dimethylprop-2-enamide Chemical compound CN(C)C(=O)C=C YLGYACDQVQQZSW-UHFFFAOYSA-N 0.000 claims description 6
- 150000003839 salts Chemical class 0.000 claims description 6
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 claims description 5
- 239000004952 Polyamide Substances 0.000 claims description 5
- 229920002647 polyamide Polymers 0.000 claims description 5
- 229920006295 polythiol Polymers 0.000 claims description 5
- 150000005846 sugar alcohols Polymers 0.000 claims description 5
- OGFKTAMJLKHRAZ-UHFFFAOYSA-N 2,2-dimethoxyacetaldehyde Chemical compound COC(OC)C=O OGFKTAMJLKHRAZ-UHFFFAOYSA-N 0.000 claims description 4
- WWMIMRADNBGDHP-UHFFFAOYSA-N 2-hydroxyhexanedial Chemical compound O=CC(O)CCCC=O WWMIMRADNBGDHP-UHFFFAOYSA-N 0.000 claims description 4
- 229920002085 Dialdehyde starch Polymers 0.000 claims description 4
- SXRSQZLOMIGNAQ-UHFFFAOYSA-N Glutaraldehyde Chemical compound O=CCCCC=O SXRSQZLOMIGNAQ-UHFFFAOYSA-N 0.000 claims description 4
- PCSMJKASWLYICJ-UHFFFAOYSA-N Succinic aldehyde Chemical compound O=CCCC=O PCSMJKASWLYICJ-UHFFFAOYSA-N 0.000 claims description 4
- 125000004985 dialkyl amino alkyl group Chemical group 0.000 claims description 4
- AHIXHWRUDZFHEZ-UHFFFAOYSA-N furan-2,3-dicarbaldehyde Chemical compound O=CC=1C=COC=1C=O AHIXHWRUDZFHEZ-UHFFFAOYSA-N 0.000 claims description 4
- 238000010348 incorporation Methods 0.000 claims description 4
- WGESLFUSXZBFQF-UHFFFAOYSA-N n-methyl-n-prop-2-enylprop-2-en-1-amine Chemical compound C=CCN(C)CC=C WGESLFUSXZBFQF-UHFFFAOYSA-N 0.000 claims description 4
- DYUWTXWIYMHBQS-UHFFFAOYSA-N n-prop-2-enylprop-2-en-1-amine Chemical compound C=CCNCC=C DYUWTXWIYMHBQS-UHFFFAOYSA-N 0.000 claims description 4
- 125000001453 quaternary ammonium group Chemical class 0.000 claims description 4
- UZNHKBFIBYXPDV-UHFFFAOYSA-N trimethyl-[3-(2-methylprop-2-enoylamino)propyl]azanium;chloride Chemical compound [Cl-].CC(=C)C(=O)NCCC[N+](C)(C)C UZNHKBFIBYXPDV-UHFFFAOYSA-N 0.000 claims description 4
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims description 3
- 229920000083 poly(allylamine) Polymers 0.000 claims description 3
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 claims description 2
- NBTXFNJPFOORGI-UHFFFAOYSA-N 2-ethenoxyethyl prop-2-enoate Chemical compound C=COCCOC(=O)C=C NBTXFNJPFOORGI-UHFFFAOYSA-N 0.000 claims description 2
- KUDUQBURMYMBIJ-UHFFFAOYSA-N 2-prop-2-enoyloxyethyl prop-2-enoate Chemical compound C=CC(=O)OCCOC(=O)C=C KUDUQBURMYMBIJ-UHFFFAOYSA-N 0.000 claims description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 claims description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 2
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 claims description 2
- 239000002202 Polyethylene glycol Substances 0.000 claims description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 2
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims description 2
- 150000008065 acid anhydrides Chemical class 0.000 claims description 2
- 125000000129 anionic group Chemical group 0.000 claims description 2
- 229920005605 branched copolymer Polymers 0.000 claims description 2
- 239000000470 constituent Substances 0.000 claims description 2
- WJMQFZCWOFLFCI-UHFFFAOYSA-N cyanomethyl prop-2-enoate Chemical compound C=CC(=O)OCC#N WJMQFZCWOFLFCI-UHFFFAOYSA-N 0.000 claims description 2
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Chemical compound CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 claims description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 2
- 239000011976 maleic acid Substances 0.000 claims description 2
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 2
- 125000005394 methallyl group Chemical group 0.000 claims description 2
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 claims description 2
- RQAKESSLMFZVMC-UHFFFAOYSA-N n-ethenylacetamide Chemical compound CC(=O)NC=C RQAKESSLMFZVMC-UHFFFAOYSA-N 0.000 claims description 2
- ZQXSMRAEXCEDJD-UHFFFAOYSA-N n-ethenylformamide Chemical compound C=CNC=O ZQXSMRAEXCEDJD-UHFFFAOYSA-N 0.000 claims description 2
- CHDKQNHKDMEASZ-UHFFFAOYSA-N n-prop-2-enoylprop-2-enamide Chemical compound C=CC(=O)NC(=O)C=C CHDKQNHKDMEASZ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052698 phosphorus Inorganic materials 0.000 claims description 2
- 229920001223 polyethylene glycol Polymers 0.000 claims description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 2
- VPYJNCGUESNPMV-UHFFFAOYSA-N triallylamine Chemical compound C=CCN(CC=C)CC=C VPYJNCGUESNPMV-UHFFFAOYSA-N 0.000 claims description 2
- OEIXGLMQZVLOQX-UHFFFAOYSA-N trimethyl-[3-(prop-2-enoylamino)propyl]azanium;chloride Chemical compound [Cl-].C[N+](C)(C)CCCNC(=O)C=C OEIXGLMQZVLOQX-UHFFFAOYSA-N 0.000 claims description 2
- NLVXSWCKKBEXTG-UHFFFAOYSA-N vinylsulfonic acid Chemical compound OS(=O)(=O)C=C NLVXSWCKKBEXTG-UHFFFAOYSA-N 0.000 claims description 2
- YZCKVEUIGOORGS-OUBTZVSYSA-N Deuterium Chemical compound [2H] YZCKVEUIGOORGS-OUBTZVSYSA-N 0.000 claims 1
- 239000003795 chemical substances by application Substances 0.000 abstract description 10
- 125000004435 hydrogen atom Chemical group [H]* 0.000 abstract 1
- 229920000642 polymer Polymers 0.000 description 43
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 15
- 230000008569 process Effects 0.000 description 14
- 239000000123 paper Substances 0.000 description 11
- 238000012360 testing method Methods 0.000 description 9
- 239000000835 fiber Substances 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 230000000704 physical effect Effects 0.000 description 5
- 239000000725 suspension Substances 0.000 description 5
- 239000004480 active ingredient Substances 0.000 description 4
- 229920005601 base polymer Polymers 0.000 description 4
- 230000006872 improvement Effects 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- 238000009749 continuous casting Methods 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000012429 reaction media Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 229920001131 Pulp (paper) Polymers 0.000 description 2
- 238000013019 agitation Methods 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000012549 training Methods 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- ZKYCLDTVJCJYIB-UHFFFAOYSA-N 2-methylidenedecanamide Chemical compound CCCCCCCCC(=C)C(N)=O ZKYCLDTVJCJYIB-UHFFFAOYSA-N 0.000 description 1
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 150000003926 acrylamides Chemical class 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 125000005250 alkyl acrylate group Chemical group 0.000 description 1
- 125000000746 allylic group Chemical group 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009172 bursting Effects 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000012669 compression test Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000013051 drainage agent Substances 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- DNJIEGIFACGWOD-UHFFFAOYSA-N ethyl mercaptane Natural products CCS DNJIEGIFACGWOD-UHFFFAOYSA-N 0.000 description 1
- 238000005189 flocculation Methods 0.000 description 1
- 230000016615 flocculation Effects 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 125000001165 hydrophobic group Chemical group 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 239000002655 kraft paper Substances 0.000 description 1
- 150000002734 metacrylic acid derivatives Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- XFHJDMUEHUHAJW-UHFFFAOYSA-N n-tert-butylprop-2-enamide Chemical compound CC(C)(C)NC(=O)C=C XFHJDMUEHUHAJW-UHFFFAOYSA-N 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 238000012667 polymer degradation Methods 0.000 description 1
- 238000012673 precipitation polymerization Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 229910001379 sodium hypophosphite Inorganic materials 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000010557 suspension polymerization reaction Methods 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- DGVVWUTYPXICAM-UHFFFAOYSA-N β‐Mercaptoethanol Chemical compound OCCS DGVVWUTYPXICAM-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/20—Macromolecular organic compounds
- D21H17/33—Synthetic macromolecular compounds
- D21H17/34—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D21H17/41—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing ionic groups
- D21H17/44—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing ionic groups cationic
- D21H17/45—Nitrogen-containing groups
- D21H17/455—Nitrogen-containing groups comprising tertiary amine or being at least partially quaternised
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/20—Macromolecular organic compounds
- D21H17/33—Synthetic macromolecular compounds
- D21H17/34—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D21H17/37—Polymers of unsaturated acids or derivatives thereof, e.g. polyacrylates
- D21H17/375—Poly(meth)acrylamide
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/28—Condensation with aldehydes or ketones
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/20—Macromolecular organic compounds
- D21H17/33—Synthetic macromolecular compounds
- D21H17/46—Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D21H17/54—Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/20—Macromolecular organic compounds
- D21H17/33—Synthetic macromolecular compounds
- D21H17/46—Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D21H17/54—Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen
- D21H17/56—Polyamines; Polyimines; Polyester-imides
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/71—Mixtures of material ; Pulp or paper comprising several different materials not incorporated by special processes
- D21H17/72—Mixtures of material ; Pulp or paper comprising several different materials not incorporated by special processes of organic material
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
- D21H21/06—Paper forming aids
- D21H21/10—Retention agents or drainage improvers
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
- D21H21/14—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
- D21H21/18—Reinforcing agents
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2800/00—Copolymer characterised by the proportions of the comonomers expressed
- C08F2800/10—Copolymer characterised by the proportions of the comonomers expressed as molar percentages
Definitions
- the invention relates to a novel paper-making process which uses as a dry strength, retention, dewatering and machinability agent a product resulting from the reaction between at least one aldehyde and at least one ( co) cationic or amphoteric base polymer, said copolymer comprising acrylamide or derivative and incorporating, within itself, at least one polyfunctional compound comprising at least 3 heteroatoms, of which at least 3 of these heteroatoms each have at least one mobile hydrogen .
- WO2011 / 15783 describes polymers obtained by Hofmann degradation reaction on a (co) polymer base.
- the base copolymer contains a polyfunctional compound incorporated at the time of polymerization of the (co) polymer base. These compounds are used in papermaking as a flocculation, retention and / or drainage agent.
- US20110056640 discloses a papermaking process using a compound resulting from the reaction between an aldehyde and an acrylamide / diallyldimethylammonium chloride copolymer. This process only improves drainage.
- WO2010 / 059946 and US2006 / 0270801 disclose a mixture of compounds for improving paper strength. These mixtures comprise a glyoxalated polymer, and optionally a polyfunctional compound.
- the document WO2005 / 072185 describes a process for producing paper using a polymer whose amine or amide functions have reacted with an aldehyde.
- WO2007 / 041380 discloses a wet strength agent consisting of a mixture of glyoxalated polymers.
- the problem to be solved by the invention is to develop a novel papermaking process in which both the dewatering properties and the physical properties of the paper are improved. Description of the invention
- the Applicant has found and developed a novel method of manufacturing a sheet of paper and / or cardboard and the like, according to which, before or after forming said sheet, the cellulosic material is brought into contact with at least one additive .
- the process is characterized in that said additive is a cationic or amphoteric (co) polymer derived from the reaction between at least one aldehyde and at least one (co) polymer base comprising at least one nonionic monomer chosen from the group comprising acrylamide (and / or methacrylamide), N, N-dimethylacrylamide, and / or acrylonitrile, said base copolymer being previously modified with at least one polyfunctional compound comprising at least 3 heteroatoms chosen from N, S, O, P, at least 3 of these heteroatoms each have at least one mobile hydrogen.
- the modification of the (co) polymer base with at least one additional polyfunctional compound consists either of incorporating the additional polyfunctional compound (s) before or during the polymerization of the constituent comonomers. of the (co) polymer base, or to graft the additional polyfunctional compound (s) onto the (co) polymer base.
- the polyfunctional compound when the polyfunctional compound is incorporated before or during the polymerization, it does not react with the nonionic monomer chosen from the group comprising acrylamide (and / or methacrylamide), N, N dimethylacrylamide, and / or acrylonitrile. Indeed, the nonionic monomer is added while the reaction medium is in the polymerization conditions.
- the polyfunctional compounds may be: oligomers, polymers, carbon chains having at least three carbon atoms.
- the polyfunctional compound may be a polymer resulting from the polymerization called "template”. These are polymers in which are introduced during their synthesis, a low molecular weight polymer that will absorb one of the monomers entering the polymerization.
- the so-called additional polyfunctional compounds are chosen from the group comprising polyethyleneimines (PEI), polyamines (primary and secondary), polyallyamines, polythiols, polyalcohols, polyamides epichlorohydrin (PAE), polyamines amides (PAA)
- the cationic or amphoteric final (co) polymer therefore comprises at least one nonionic monomer chosen from the group comprising acrylamide (and / or methacrylamide), N, N-dimethylacrylamide and / or acrylonitrile, and is modified, prior to the reaction with an aldehyde compound, at least one additional polymer selected from the group consisting of polyethyleneimine, polyamine (primary or secondary), polyallylamine, polythiols, polyalcohols, polyamides epichlorohydrin (PAE), polyamines amides (PAA).
- the incorporated polyfunctional compound is selected from the group consisting of polyethyleneimine (PEI) and polyamine amide (PAA).
- the (co) polymer base contains at least 100 ppm of polyfunctional polymer, preferably at least 500 ppm, more preferably at least 1000 ppm.
- the aldehyde may be chosen from the group comprising glyoxal, glutaraldehyde, furan-dialdehyde, 2-hydroxyadipaldehyde, succinaldehyde, dialdehyde starch, 2,2-dimethoxyethanal, diepoxy compounds, and combinations thereof.
- the aldehyde compound will be glyoxal.
- the (co) base polymer is branched by means of a radical branching agent.
- the resulting copolymer is reacted with glyoxal.
- the branching may preferably be carried out during the polymerization of the base copolymer, in the presence of a polyfunctional radical branching agent and optionally of a transfer agent.
- branching agents methylene bisacrylamide (MBA), ethylene glycol di-acrylate, polyethylene glycol dimethacrylate, diacrylamide, cyanomethylacrylate, vinyloxyethylacrylate or methacrylate, triallylamine,
- the branching agent is advantageously introduced at a rate of from five to fifty thousand (5 to 50,000) parts per million by weight relative to the active ingredient, preferably from 5 to 10,000, advantageously from 5 to 5,000.
- the branching agent is methylenebisacrylamide (MBA).
- transfer agents isopropyl alcohol, sodium hypophosphite, mercaptoethanol, etc.
- the process can be used successfully for the manufacture of paper and paperboard packaging, paper coating media, sanitary and household papers, of any type of paper, paperboard or the like requiring the use of a polymer as a dry strength, retention, dewatering and machinability agent. Machinability means optimizing the operation of the paper machine by increasing productivity by better dripping on the table, better dryness at the press section, a reduction of breakages by a cleaner circuits and a decrease deposits.
- the method also makes it possible to obtain good drainage properties and good physical properties (improvement of bursting, breaking length, ring crush test, short span compression test, concora medium test, internal cohesion, wet break length).
- the final cationic or amphoteric copolymer used in the process of the invention has a cationic charge density preferably greater than 0.4 meq / g and advantageously greater than 1.25 meq / g.
- the cationic or amphoteric (co) polymer is derived from the reaction between: 1 to 30% by weight of at least one aldehyde preferably chosen from the group comprising glyoxal, glutaraldehyde, furan-dialdehyde, 2- hydroxyadipaldehyde, succinaldehyde, dialdehyde starch, 2,2-dimethoxyethanal, diepoxy compounds, and combinations thereof,
- a nonionic monomer chosen from the group comprising acrylamide (and / or methacrylamide), N, N-dimethylacrylamide and / or acrylonitrile, preferably acrylamide, at least 100 ppm at least one additional polyfunctional compound chosen from the group comprising polyethyleneimine, polyamine (primary or secondary), polyallylamine, polythiols, polyalcohols, polyamides epichlorohydrin (PAE), polyamines amides (PAA) advantageously polyethyleneimine,
- o optionally at least:
- unsaturated cationic ethylenic monomer preferably selected from the group consisting of dialkylaminoalkyl (meth) acrylamide, diallylamine, methyldiallylamine and their quaternary ammonium or acid salts.
- dialkylaminoalkyl (meth) acrylamide diallylamine
- methyldiallylamine methyldiallylamine
- their quaternary ammonium or acid salts quaternary ammonium or acid salts.
- DMAC dimethyldiallylammonium chloride
- APITAC acrylamidopropyltrimethylammonium chloride
- MATAC methacrylamidopropyltrimethylammonium chloride
- ⁇ and / or a nonionic monomer preferably selected from the group consisting of N-vinyl acetamide, N-vinylformamide, N-vinylpyrrolidone and / or vinyl acetate, ⁇ and / or an anionic monomer or acid anhydride selected from the group consisting of (meth) acrylic acid, sulfonic acrylamidomethylpropyl acid, itaconic acid, maleic anhydride, maleic acid, methallyl acid sulfonic acid, vinylsulfonic acid and their salts.
- the final cationic or amphoteric (co) polymer is derived from the reaction preferably:
- a radical branching agent by means of a radical branching agent and comprising:
- At least one unsaturated cationic ethylenic comonomer selected from the group consisting of dialkylaminoalkyl (meth) acrylamide, diallylamine, methyldiallylamine and their quaternary ammonium or acid salt monomers, preferably dimethyldiallylammonium chloride,
- water-insoluble monomers such as acrylic, allylic or vinyl monomers having a hydrophobic group.
- these monomers will be used in very small amounts, less than 20 mole%, preferably less than 10 mole%, and they will be chosen preferentially from the group comprising acrylamide derivatives such as N-alkylacrylamide by for example N-tert-butylacrylamide, octylacrylamide and ⁇ , ⁇ -dialkylacrylamides such as ⁇ , ⁇ -dihexylacrylamide ... acrylic acid derivatives such as alkyl acrylates and methacrylates ...
- the base copolymer used in the invention is a copolymer of a nonionic monomer and a cationic monomer.
- the incorporation of the additional polyfunctional compound modifying the structure of the (co) polymer base can be done in the reaction medium before or during polymerization, or by any other grafting method on the finished base copolymer.
- the polyfunctional compound does not react with the monomers until they are polymerized.
- the additional polyfunctional compound will be mixed with a comonomer before polymerization.
- the amount of final (co) polymer introduced into the fibrous suspension is between 500 and 4000 grams of active polymer per tonne of dry pulp (g / t).
- the quantity introduced is between 1000 g / t and 3000 g / t.
- the (co) polymer base does not require the development of a particular polymerization process.
- the main polymerization techniques are: precipitation polymerization, emulsion polymerization (aqueous or inverse) followed or not by a distillation step and / or spray drying, and suspension polymerization or solution polymerization, both of which are preferred.
- Glyoxalation does not require any particular method.
- the main glyoxalation techniques known to those skilled in the art can be used.
- the pH may be adjusted after addition of glyoxal with a sodium hydroxide solution. It is also possible to conduct the reaction at controlled pH by continuous addition of sodium hydroxide, but also to add the glyoxal in several fractions. The progress of the reaction may also be followed by a measurement of viscosity, turbidity, etc.
- the additive is added to the process, before or after forming the sheet.
- the contacting of the cellulosic material with the additive can be carried out in different ways.
- the final (co) polymer may be used as a dilute or undiluted aqueous solution. It will be added to the cellulosic material. It may be applied by an impregnation technique, or may be added directly to the fibrous suspension at any point in the papermaking process where usually dry strength agents are introduced. It can be introduced into thick stock or thin stock. It can be added at the level of the fan pump or the headbox. Preferably the (co) polymer will be introduced before the headbox. It may also be at the level of the training table or press size, for example by spray.
- the final (co) polymer is injected industrially into the fibrous suspension, i.e. before dilution with white water (thick paste).
- concentrations of the dough are of the order of 3% and 5%.
- the process can be used with virgin fiber pulps (Kraft, Bisulfite ..), recycled fibers, de-inked pastes, mechanical and thermo mechanical pulps.
- the final (co) polymer may be prepared near the paper machine.
- the polymers of the invention identified among polymers 1 to 17 were obtained from a PEI-modified base copolymer during polymerization according to the following protocol .
- the examples were carried out with a copolymer acrylamide and dimethyldiallyl ammonium chloride (DADMAC), branched with MBA (1000 ppm / active ingredient), modified with a polyethyleneimine polymer (BASF type Polymin HM), up to 1% compared to the active ingredient.
- DADMAC dimethyldiallyl ammonium chloride
- MBA 1000 ppm / active ingredient
- BASF type Polymin HM polyethyleneimine polymer
- the acrylamide will be incorporated in continuous casting for 2 hours, in a reaction medium maintained at 85 ° C.
- Catalysis will be SPS and MBS, catalysts well known to those skilled in the art.
- the examples (polymers 19 and 20) were carried out in the same manner as above, with the difference that the polyethyleneimine is not mixed with the monomer in the reactor. To do this, the polyethyleneimine is added to the reactor after the polymerization at a level of 1% relative to the active ingredient.
- the grafting is by catalysis using 1500 ppm of SPS in continuous casting for lh30.
- the pH can be adjusted after adding glyoxal with 10% sodium hydroxide solution. It is possible to conduct the reaction at controlled pH by continuous addition of 10% sodium hydroxide, but also to add the glyoxal in several fractions.
- the viscometer used is Brookfield type, with a LV1 module and a speed of 60 rpm. Preparation of the dough
- the paste used consists of recycled cardboard fibers.
- the pulp is prepared by disintegrating for 90 minutes 90 grams of recycled fibers in 2 liters of hot water.
- the Shopper degree of the dough thus obtained is 43.
- the tests are carried out with the paste at neutral pH.
- the paste obtained is then diluted to a total volume of 9 liters. Once the consistency measured accurately, the necessary amount of this paste is taken so as to ultimately obtain a sheet with a basis weight of 120g / m2.
- T 30s: Stopping the agitation and recovery of the liter of dough. Realization of the TAPPI T 2270M-94 test.
- the paper forms are made with an automatic dynamic form.
- the paste is introduced into the cuvier of the dynamic form, diluted to a consistency of 0.32% and stirred moderately with a mechanical stirrer to homogenize the fibrous suspension.
- the dough is pumped to the nozzle level to prime the circuit.
- a blotter and training cloth are placed in the bowl of the dynamic formette before starting the rotation of the bowl at 900m / min and constructing the water wall.
- the final copolymer is then introduced into the stirred fibrous suspension with a contact time of 30 seconds.
- the sheet is then made (in automatic mode) by 22 round-trips of the nozzle projecting the paste in the wall of water.
- the forming web with the formed fiber network is removed from the dynamically shaped bowl and placed on a table.
- a dry blotter is deposited on the side of the wet fiber mat and is pressed once with a roll. The whole is returned and the fabric is delicately separated from the fibrous mat.
- a second dry blotter is deposited and the sheet (between the two blotters) is pressed once under a press delivering 4 bars and is then dried on a dryer stretched for 9 min at 107 ° C. The two blotters are then removed and the sheet is stored overnight in a room with controlled humidity and temperature (50% relative humidity and 23 ° C). The dry strength properties of all the sheets obtained by this procedure are then evaluated.
- Burst test Burst index is measured with a Messmer Buchel M 405 burst (average of 14 measurements). The test is performed according to TAPPI standard T403 OM 91
- the sheets of paper are made according to the above procedure by introducing the final copolymer at a dosage of 2.5 kg / T (dry polymer / dry fiber).
- the branching alone of the glyoxalated base copolymer and free of PEI (polymer 3) makes it possible to obtain an improvement in drainage performance, but is detrimental to the improvement of the physical properties.
- the method of the invention makes it possible to obtain an improvement of drainage superior to other products while maintaining or even while improving the dry physical properties.
- the table above shows the evolution of the results with respect to the increase of the cationicity of the base polymer.
- the polymers of the invention are all better than the polymer 9.
- polymers 10 and 14 exhibit different performance.
- Polymer 14 which has a cationicity of 40 mole%, gives superior results whether in drip or burst (Burst Index) to polymer 10 (5 mole% cationicity).
- the polymer 17 corresponds to Example 7 of the patent US20110056640 which was reproduced and then tested.
- Polymers 19 and 20 were made from the (co) polymer base with post-grafting of PEI. More specifically, the polymerization of acrylamide and DADMAC is carried out in the presence of MBA. The polymer obtained is then separated into three fractions.
- the first fraction reacts with glyoxal as previously described: Sample 18.
- PEI and an initiator are added in continuous casting for 90 minutes at 80 ° C for the purpose of post-grafting the PEI.
- SPS initiator
- the third fraction was treated in the same way as for sample 19, but without the addition of PEI.
- the goal is to evaluate the impact of the continuous addition of the SPS. Gloxalation is identical to Examples 18 and 19.
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Paper (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
Description
Claims
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR1251740A FR2987375A1 (en) | 2012-02-27 | 2012-02-27 | NOVEL PAPERMAKING PROCESS USING A BASIC COPOLYMER HAVING REACTED WITH ALDEHYDE AS DRY RESISTANCE, RETENTION, DRIP, AND MACHINABILITY AGENT |
PCT/FR2013/050390 WO2013128109A1 (en) | 2012-02-27 | 2013-02-26 | Novel method for producing paper implementing a base copolymer having reacted with an aldehyde as a dry strength, retention, drainage and machinability agent |
Publications (2)
Publication Number | Publication Date |
---|---|
EP2820188A1 true EP2820188A1 (en) | 2015-01-07 |
EP2820188B1 EP2820188B1 (en) | 2016-12-07 |
Family
ID=48014064
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP13712850.0A Active EP2820188B1 (en) | 2012-02-27 | 2013-02-26 | Novel method for producing paper implementing a base copolymer having reacted with an aldehyde as a dry strength, retention, drainage and machinability agent |
Country Status (9)
Country | Link |
---|---|
US (2) | US9506200B2 (en) |
EP (1) | EP2820188B1 (en) |
KR (1) | KR102157401B1 (en) |
CN (1) | CN104093900B (en) |
BR (1) | BR112014017918B1 (en) |
CA (1) | CA2862995C (en) |
ES (1) | ES2609676T3 (en) |
FR (1) | FR2987375A1 (en) |
WO (1) | WO2013128109A1 (en) |
Families Citing this family (15)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US9752283B2 (en) | 2007-09-12 | 2017-09-05 | Ecolab Usa Inc. | Anionic preflocculation of fillers used in papermaking |
US8088250B2 (en) | 2008-11-26 | 2012-01-03 | Nalco Company | Method of increasing filler content in papermaking |
CN103132383B (en) * | 2011-11-25 | 2017-04-12 | 纳尔科公司 | Sizing agent pretreatment for improving paper strength accessory ingredient performance in papermaking |
FR2987375A1 (en) | 2012-02-27 | 2013-08-30 | Snf Sas | NOVEL PAPERMAKING PROCESS USING A BASIC COPOLYMER HAVING REACTED WITH ALDEHYDE AS DRY RESISTANCE, RETENTION, DRIP, AND MACHINABILITY AGENT |
AT518624B1 (en) * | 2016-04-25 | 2018-10-15 | Applied Chemicals Handels Gmbh | Process for the preparation of a dry strength agent, in particular of glyoxylated polyacrylamide |
MX2018015283A (en) | 2016-06-10 | 2019-04-09 | Ecolab Usa Inc | Low molecular weight dry powder polymer for use as paper-making dry strength agent. |
EP3662108A1 (en) | 2017-07-31 | 2020-06-10 | Ecolab Usa Inc. | Dry polymer application method |
CN111373325B (en) * | 2017-11-21 | 2023-10-17 | 东丽株式会社 | Silicone resin composition, cured film, and display device |
CN111315814B (en) | 2017-12-13 | 2023-01-20 | 埃科莱布美国股份有限公司 | Solution comprising associative polymer and cyclodextrin polymer |
CN108424494A (en) * | 2018-01-04 | 2018-08-21 | 苏州派凯姆新能源科技股份有限公司 | A kind of preparation method of the amphoteric resin of acetaldehyde and its application in papermaking |
CN108611924A (en) * | 2018-04-11 | 2018-10-02 | 南安市创培电子科技有限公司 | A kind of environment protection three-dimensional answers the production method of line wrapping paper |
FR3094980B1 (en) | 2019-04-10 | 2021-04-09 | S N F Sa | NEW ADDITIVE BASED ON WATER-SOLUBLE POLYMERS AND ITS USES |
EP4201967B1 (en) * | 2021-12-22 | 2024-02-07 | SNF Group | Device and method for preparing an aldehyde-functionalised polymer |
KR20230159906A (en) | 2022-05-16 | 2023-11-23 | 안희태 | How to wirelessly transmit sensor information from a bow target |
FR3137093B1 (en) | 2022-06-24 | 2024-06-14 | Snf Sa | Water-soluble polymer and its preparation process |
Family Cites Families (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR2692292B1 (en) * | 1992-06-11 | 1994-12-02 | Snf Sa | Method for manufacturing paper or cardboard with improved retention. |
JPH09228295A (en) * | 1996-02-22 | 1997-09-02 | Seiko Kagaku Kogyo Co Ltd | Paper-processing agent |
US7641766B2 (en) * | 2004-01-26 | 2010-01-05 | Nalco Company | Method of using aldehyde-functionalized polymers to enhance paper machine dewatering |
US7897013B2 (en) * | 2004-08-17 | 2011-03-01 | Georgia-Pacific Chemicals Llc | Blends of glyoxalated polyacrylamides and paper strengthening agents |
US7828934B2 (en) * | 2004-12-21 | 2010-11-09 | Hercules Incorporated | Reactive cationic resins for use as dry and wet strength agents in sulfite ion-containing papermaking systems |
US7589153B2 (en) * | 2005-05-25 | 2009-09-15 | Georgia-Pacific Chemicals Llc | Glyoxalated inter-copolymers with high and adjustable charge density |
US7608665B2 (en) * | 2005-09-30 | 2009-10-27 | Lanxess Corporation | Temporary wet strength resin for paper applications |
WO2008011138A1 (en) * | 2006-07-21 | 2008-01-24 | Bercen Incorporated | Paper making process using cationic polyacrylamides and crosslinking compositions for use in same |
US7863395B2 (en) * | 2006-12-20 | 2011-01-04 | Georgia-Pacific Chemicals Llc | Polyacrylamide-based strengthening agent |
FR2948941B1 (en) * | 2009-08-04 | 2011-10-28 | Snf Sas | CATIONIC COPOLYMERS DERIVED FROM ACRYLAMIDE AND USES THEREOF |
FR2987375A1 (en) | 2012-02-27 | 2013-08-30 | Snf Sas | NOVEL PAPERMAKING PROCESS USING A BASIC COPOLYMER HAVING REACTED WITH ALDEHYDE AS DRY RESISTANCE, RETENTION, DRIP, AND MACHINABILITY AGENT |
-
2012
- 2012-02-27 FR FR1251740A patent/FR2987375A1/en not_active Withdrawn
-
2013
- 2013-02-26 KR KR1020147021165A patent/KR102157401B1/en active IP Right Grant
- 2013-02-26 CN CN201380006950.9A patent/CN104093900B/en active Active
- 2013-02-26 CA CA2862995A patent/CA2862995C/en active Active
- 2013-02-26 EP EP13712850.0A patent/EP2820188B1/en active Active
- 2013-02-26 ES ES13712850.0T patent/ES2609676T3/en active Active
- 2013-02-26 BR BR112014017918-2A patent/BR112014017918B1/en active IP Right Grant
- 2013-02-26 WO PCT/FR2013/050390 patent/WO2013128109A1/en active Application Filing
- 2013-02-26 US US14/373,069 patent/US9506200B2/en active Active
-
2016
- 2016-10-18 US US15/296,756 patent/US10132039B2/en active Active
Also Published As
Publication number | Publication date |
---|---|
BR112014017918B1 (en) | 2021-06-01 |
EP2820188B1 (en) | 2016-12-07 |
KR102157401B1 (en) | 2020-09-17 |
CA2862995C (en) | 2020-06-02 |
CN104093900B (en) | 2016-09-21 |
BR112014017918A2 (en) | 2020-06-23 |
FR2987375A1 (en) | 2013-08-30 |
US10132039B2 (en) | 2018-11-20 |
US20170037575A1 (en) | 2017-02-09 |
KR20140138117A (en) | 2014-12-03 |
US9506200B2 (en) | 2016-11-29 |
CN104093900A (en) | 2014-10-08 |
US20150136348A1 (en) | 2015-05-21 |
ES2609676T3 (en) | 2017-04-21 |
CA2862995A1 (en) | 2013-09-06 |
WO2013128109A1 (en) | 2013-09-06 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
EP2820188B1 (en) | Novel method for producing paper implementing a base copolymer having reacted with an aldehyde as a dry strength, retention, drainage and machinability agent | |
EP2462281B1 (en) | Acrylamide-derived cationic copolymers and their uses | |
WO2008107620A2 (en) | Acrylamide-derived cationic copolymers and uses of same | |
RU2361977C2 (en) | Method of applying polymers functioning as aldehyde to improve drying in papermaking machines | |
EP1838923B1 (en) | Method of producing high dry strength paper and cardboard and paper and cardboard thus obtained | |
EP1851380B1 (en) | Method for making paper and cardboard with high dry strength and resulting papers and cardboards | |
WO2009013423A2 (en) | Water-soluble post-branched cationic acrylamide polymers and use thereof | |
EP3094658A1 (en) | Aqueous solution of cationic copolymers derived from acrylamide, preparation method and use | |
EP2870287B1 (en) | Improved method for manufacturing paper using a cationic polymer obtained by hofmann degradation | |
EP3774948A1 (en) | Method for producing anionic polymers and use as resistance agents in a paper-making method | |
WO2019215413A1 (en) | Complex of polymers, preparation and use | |
EP3722330B1 (en) | New additive made of water-soluble polymers and uses thereof |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
|
17P | Request for examination filed |
Effective date: 20140730 |
|
AK | Designated contracting states |
Kind code of ref document: A1 Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR |
|
AX | Request for extension of the european patent |
Extension state: BA ME |
|
DAX | Request for extension of the european patent (deleted) | ||
17Q | First examination report despatched |
Effective date: 20151002 |
|
GRAP | Despatch of communication of intention to grant a patent |
Free format text: ORIGINAL CODE: EPIDOSNIGR1 |
|
INTG | Intention to grant announced |
Effective date: 20160811 |
|
GRAS | Grant fee paid |
Free format text: ORIGINAL CODE: EPIDOSNIGR3 |
|
GRAA | (expected) grant |
Free format text: ORIGINAL CODE: 0009210 |
|
AK | Designated contracting states |
Kind code of ref document: B1 Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR |
|
REG | Reference to a national code |
Ref country code: GB Ref legal event code: FG4D Free format text: NOT ENGLISH |
|
REG | Reference to a national code |
Ref country code: CH Ref legal event code: EP Ref country code: AT Ref legal event code: REF Ref document number: 851828 Country of ref document: AT Kind code of ref document: T Effective date: 20161215 |
|
REG | Reference to a national code |
Ref country code: IE Ref legal event code: FG4D Free format text: LANGUAGE OF EP DOCUMENT: FRENCH |
|
REG | Reference to a national code |
Ref country code: DE Ref legal event code: R096 Ref document number: 602013015003 Country of ref document: DE |
|
REG | Reference to a national code |
Ref country code: SE Ref legal event code: TRGR |
|
REG | Reference to a national code |
Ref country code: FR Ref legal event code: PLFP Year of fee payment: 5 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: LV Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20161207 |
|
REG | Reference to a national code |
Ref country code: LT Ref legal event code: MG4D |
|
REG | Reference to a national code |
Ref country code: NL Ref legal event code: MP Effective date: 20161207 |
|
REG | Reference to a national code |
Ref country code: ES Ref legal event code: FG2A Ref document number: 2609676 Country of ref document: ES Kind code of ref document: T3 Effective date: 20170421 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: LT Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20161207 Ref country code: GR Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20170308 Ref country code: NO Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20170307 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: BE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20170228 Ref country code: RS Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20161207 Ref country code: HR Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20161207 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: NL Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20161207 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: CZ Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20161207 Ref country code: EE Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20161207 Ref country code: SK Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20161207 Ref country code: RO Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20161207 Ref country code: IS Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20170407 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: SM Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20161207 Ref country code: PT Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20170407 Ref country code: BG Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20170307 Ref country code: PL Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20161207 |
|
REG | Reference to a national code |
Ref country code: DE Ref legal event code: R097 Ref document number: 602013015003 Country of ref document: DE |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: MC Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20161207 |
|
REG | Reference to a national code |
Ref country code: CH Ref legal event code: PL |
|
PLBE | No opposition filed within time limit |
Free format text: ORIGINAL CODE: 0009261 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: LI Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20170228 Ref country code: CH Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20170228 |
|
26N | No opposition filed |
Effective date: 20170908 |
|
REG | Reference to a national code |
Ref country code: IE Ref legal event code: MM4A |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: DK Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20161207 Ref country code: SI Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20161207 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: LU Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20170226 |
|
REG | Reference to a national code |
Ref country code: BE Ref legal event code: MM Effective date: 20170228 |
|
REG | Reference to a national code |
Ref country code: FR Ref legal event code: PLFP Year of fee payment: 6 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: IE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20170226 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: MT Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20161207 |
|
REG | Reference to a national code |
Ref country code: AT Ref legal event code: UEP Ref document number: 851828 Country of ref document: AT Kind code of ref document: T Effective date: 20161207 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: HU Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT; INVALID AB INITIO Effective date: 20130226 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: CY Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20161207 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: MK Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20161207 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: AL Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20161207 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: FI Payment date: 20220118 Year of fee payment: 10 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: TR Payment date: 20220214 Year of fee payment: 10 Ref country code: SE Payment date: 20220216 Year of fee payment: 10 Ref country code: ES Payment date: 20220303 Year of fee payment: 10 |
|
P01 | Opt-out of the competence of the unified patent court (upc) registered |
Effective date: 20230527 |
|
REG | Reference to a national code |
Ref country code: SE Ref legal event code: EUG |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: SE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20230227 Ref country code: FI Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20230226 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: AT Payment date: 20240124 Year of fee payment: 12 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: ES Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20230227 |
|
REG | Reference to a national code |
Ref country code: ES Ref legal event code: FD2A Effective date: 20240426 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: ES Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20230227 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: DE Payment date: 20240213 Year of fee payment: 12 Ref country code: GB Payment date: 20240221 Year of fee payment: 12 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: IT Payment date: 20240206 Year of fee payment: 12 Ref country code: FR Payment date: 20240227 Year of fee payment: 12 |